Method of electrolytic deposition of an intrinsically conductive polymer upon a non-conductive substrate

Abstract

A capacitor and method for manufacturing the capacitor. The capacitor comprises an anode; a dielectric oxide layer coated on the anode and a plurality of conductive islands coated on the dielectric oxide layer. An organic conductive cathode is coated on the dielectric layer and conductive islands.

Claimed is:  
     
         1 . A method for forming a capacitor comprising: 
 forming an oxide layer on a valve metal;    contacting said oxide layer with a solution comprising a monomer precursor of the polymer of Formula I:                           wherein: 
 X is S, Se or N;  
 R 1  and R 2  are not hydrogen;  
   and a compound of Formula II:   R 4 —OSO 3 Na  FORMULA II   wherein R 4  is a C 3 -C 20  linear or branched alkyl; and    polymerizing said monomer.    
     
     
         2 . The method for forming a capacitor of  claim 1  wherein: 
 R 1  and R 2  independently represent linear or branched C 1 -C 16  alkyl or C 2 -C 18  alkoxyalkyl; 
 or are C 3 -C 8  cycloalkyl, phenyl or benzyl which are unsubstituted or substituted by C 1 -C 6  alkyl, C 1 -C 6  alkoxy, halogen or OR 3 ; or R 1  and R 2 , taken together, are linear C 1 -C 6  alkylene which is unsubstituted or substituted by C 1 -C 6  alkyl, C 1 -C 6  alkoxy, halogen, C 3 -C 8  cycloalkyl, phenyl, benzyl, C 1 -C 4  alkylphenyl, C 1 -C 4  alkoxyphenyl, halophenyl, C 1 -C 4  alkylbenzyl, C 1 -C 4  alkoxybenzyl or halobenzyl, 5-, 6-, or 7-membered heterocyclic structure containing two oxygen elements;  
 
 R 3  represents hydrogen, linear or branched C 1 -C 16  alkyl or C 2 -C 18  alkoxyalkyl; or are C 3 -C 8  cycloalkyl, phenyl or benzyl which are unsubstituted or substituted by C 1 -C 6  alkyl.  
 
     
     
         3 . The method for forming a capacitor of  claim 2  wherein said R 1  and R 2  are taken together to form O—CH 2  CH 2 —O.  
     
     
         4 . The method for forming a capacitor of  claim 1  further comprising electrolytic deposition of said monomer on said oxide layer during said contacting.  
     
     
         5 . The method for forming a capacitor of  claim 1  further comprising applying a seed layer on said oxide layer prior to said contacting.  
     
     
         6 . The method for forming a capacitor of  claim 5  wherein said seed layer comprises manganese dioxide.  
     
     
         7 . The method for forming a capacitor of  claim 5  wherein said seed layer covers at least about 1% of said oxide layer.  
     
     
         8 . The method for forming a capacitor of  claim 5  wherein said seed layer covers no more than about 80% of said oxide layer.  
     
     
         9 . The method for forming a capacitor of  claim 1  wherein said solution comprises about 4%, by weight, to about 17%, by weight, said compound.  
     
     
         10 . The method for forming a capacitor of  claim 1  wherein said solution comprises about 2%, by weight, to about 10%, by weight, said monomer.  
     
     
         11 . The method for forming a capacitor of  claim 10  wherein said solution comprises at least about 4%, by weight, said monomer.  
     
     
         12 . The method for forming a capacitor of  claim 10  wherein said solution comprises no more than about 5%, by weight, said monomer.  
     
     
         13 . The method for forming a capacitor of  claim 1  wherein said R 4  is a linear alkyl of 10-14 carbons.  
     
     
         14 . The method for forming a capacitor of  claim 1  wherein said valve metal is selected from a group consisting of niobium, aluminum, tantalum, titanium, zirconium, hafnium and tungsten.  
     
     
         15 . The method for forming a capacitor of  claim 1  wherein said valve metal is selected from a group consisting of niobium, aluminum and tantalum.  
     
     
         16 . A capacitor formed by the method of  claim 1 .  
     
     
         17 . A method for forming a capacitor comprising: 
 forming a valve metal into a shape to form an anode;    contacting said anode with an oxidizing solution to form a dielectric layer on said anode;    forming a discontinuous seed layer on said dielectric layer to form a mixed oxide surface;    contacting said mixed oxide surface with an aqueous solution comprising a monomer precursor to the polymer of Formula I:                          wherein R 1  and R 2  independently represent hydrogen, linear or branched C 1 -C 16  alkyl or C 2 -C 18  alkoxyalkyl; or are C 3 -C 8  cycloalkyl, phenyl or benzyl which are unsubstituted or substituted by C 1 -C 6  alkyl, C 1 -C 6  alkoxy or halogen; or R 1  and R 2 , taken together, are linear C 1 -C 6  alkylene which is unsubstituted or substituted by C 1 -C 6  alkyl, C 1 -C 6  alkoxy, halogen, C 3 -C 8  cycloalkyl, phenyl, benzyl, C 1 -C 4  alkylphenyl, C 1 -C 4  alkoxyphenyl, halophenyl, C 1 -C 4  alkylbenzyl, C 1 -C 4  alkoxybenzyl or halobenzyl, 5-, 6-, or 7-membered heterocyclic structure containing two oxygen elements;    and a compound of Formula II:   R 3 —OSO 3 Na  FORMULA II   wherein R 3  is a C 3 -C 20  linear or branched alkyl; and    electrolytically depositing and polymerizing said monomer from said solution to said mixed oxide surface.    
     
     
         18 . The method for forming a capacitor of  claim 17  wherein said seed layer comprises manganese dioxide.  
     
     
         19 . The method for forming a capacitor of  claim 17  wherein said seed layer covers at least 1% of said dielectric layer.  
     
     
         20 . The method for forming a capacitor of  claim 17  wherein said seed layer covers no more than about 80% of said dielectric layer.  
     
     
         21 . The method for forming a capacitor of  claim 17  wherein said solution comprises about 4%, by weight, to about 17%, by weight, said compound.  
     
     
         22 . The method for forming a capacitor of  claim 17  wherein said solution comprises about 2%, by weight, to about 10%, by weight, said monomer.  
     
     
         23 . The method for forming a capacitor of  claim 22  wherein said solution comprises at least about 4%, by weight, said monomer.  
     
     
         24 . The method for forming a capacitor of  claim 22  wherein said solution comprises no more than about 5%, by weight, said monomer.  
     
     
         25 . The method for forming a capacitor of  claim 17  wherein said R 1  and R 2  are taken together to form O—CH 2  CH 2 —O.  
     
     
         26 . The method for forming a capacitor of  claim 17  wherein said R 4  is a linear alkyl of 10-14 carbons.  
     
     
         27 . The method for forming a capacitor of  claim 17  wherein said valve metal is selected from a group consisting of niobium, aluminum, tantalum, titanium, zirconium, hafnium and tungsten.  
     
     
         28 . The method for forming a capacitor of  claim 27  wherein said valve metal is selected from a group consisting of niobium, aluminum and tantalum.  
     
     
         29 . A capacitor formed by the method of  claim 17 .  
     
     
         30 . A capacitor comprising: 
 an anode;    a dielectric oxide layer coated on said anode;    a plurality of conductive islands coated on said dielectric oxide layer;    an organic conductive cathode coated on said dielectric layer and said conductive islands.    
     
     
         31 . The capacitor of  claim 30  wherein said organic conductive cathode comprises a polymer formed by the electrolytic polymerization of:  
       
         
           
           
               
               
           
         
         wherein:  
         X is S, Se or N;  
         R 1  and R 2  are not hydrogen.  
       
     
     
         32 . The capacitor of  claim 30  wherein said organic conductor comprises a dopant.  
     
     
         33 . The capacitor of  claim 32  wherein said dopant is an organic sulfate.  
     
     
         34 . The capacitor of  claim 33  wherein said dopant is: 
       R 4 —OSO 3 Na 
       wherein R 4  is a C 3 -C 20  linear or branched alkyl.  
     
     
         35 . The capacitor of  claim 31  wherein X is S.  
     
     
         36 . The capacitor of  claim 31  wherein R 1  and R 2  independently represent linear or branched C 1 -C 16  alkyl or C 2 -C 18  alkoxyalkyl; or are C 3 -C 8  cycloalkyl, phenyl or benzyl which are unsubstituted or substituted by C 1 -C 6  alkyl, C 1 -C 6  alkoxy, halogen or OR 3 ; or R 1  and R 2 , taken together, are linear C 1 -C 6  alkylene which is unsubstituted or substituted by C 1 -C 6  alkyl, C 1 -C 6  alkoxy, halogen, C 3 -C 8  cycloalkyl, phenyl, benzyl, C 1 -C 4  alkylphenyl, C 1 -C 4  alkoxyphenyl, halophenyl, C 1 -C 4  alkylbenzyl, C 1 -C 4  alkoxybenzyl or halobenzyl, 5-, 6-, or 7-membered heterocyclic structure containing two oxygen elements. R 3  preferably represents hydrogen, linear or branched C 1 -C 16  alkyl or C 2 -C 18  alkoxyalkyl; or are C 3 -C 8  cycloalkyl, phenyl or benzyl which are unsubstituted or substituted by C 1 -C 6  alkyl.  
     
     
         37 . The capacitor of  claim 36  wherein said R 1  and R 2  are taken together to form O—CH 2  CH 2 —O.  
     
     
         38 . The capacitor of  claim 30  wherein said valve metal is selected from a group consisting of niobium, aluminum, tantalum, titanium, zirconium, hafnium and tungsten.  
     
     
         39 . The capacitor of  claim 38  wherein said valve metal is selected from a group consisting of niobium, aluminum and tantalum.